Past, Present and Future of the Russian Synthetic Carbohydrate Chemistry Leonid O. Kononov N. D. Zelinsky Institute of Organic Chemistry Russian Academy. - презентация

1 Past, Present and Future of the Russian Synthetic Carbohydrate Chemistry Leonid O. Kononov N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow RUSSIA

2 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 2 April 3, 2003, Rostock N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, Moscow, RUSSIA Host Institute

3 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 3 April 3, 2003, Rostock N. D. Zelinsky Institute of Organic Chemistry Established in 1934 The list of Directors of the Institute: A. E. Favorsky ( ) A. N. Nesmeyanov ( ) B. A. Kazansky ( ) N. K. Kochetkov ( ) V. A. Tartakovsky ( ) One of the largest centers of fundamental research in: organic chemistry catalysis chemistry of natural and biologically active compounds More than 500 employees Host Institute

4 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 4 April 3, 2003, Rostock Division of Physical and synthetic organic chemistry – N 3 Laboratory of Heterocyclic Compounds N 3 – N 4 Laboratory for High Pressure Research N 4 – N 5 Laboratory for Carbene Chemistry and Small-sized Cyclic Compounds N 5 – N 7 Laboratory of Polyunsaturated Compounds N 7 – N 9 Laboratory for Electrochemical Research N 9 – N10 Laboratory of Organoboron Compounds (Carbocyclic Compounds) N10 – N11 Nazarov Laboratory of Fine Organic Synthesis N11 – N12 Laboratory for Organic Synthesis N12 – N13 Laboratory for Studies of Homolytic Reactions N13 – N15 Optical Laboratory N15 – N16 Laboratory of Polymer Chemistry N16 – N17 Laboratory of Technical Chemistry and Technology N17 – N18 Laboratory of Aliphatic Compounds N18 – N19 Laboratory of Nitrogen-Containing Substances N19 – N23 Laboratory for the Chemistry of the Carbonyl Function N23 – N25 Laboratory of Chemistry of Heterofunctional Compounds N25 – N37 Laboratory of Electroorganic Synthesis N37 – N38 Laboratory of Physical-Chemical Methods of Study of Organic Compounds N38 – N42 Laboratory of Nitrocompounds N42 – N48 Laboratory of Organic Ligands N48 – N57 Laboratory of Gas Phase Organic Ions Chemistry N57 Division of Organic Chemistry of NatНural Compounds Division of Organic Chemistry of NatНural Compounds – N21 Laboratory of Carbohydrate Chemistry N21 – N22 Laboratory of Steroid and Terpenoid Chemistry N22 – N41 Laboratory of Plant Polysaccharides N41 – N55 Laboratory for Modification of Natural and Synthetic Polymers N55 Division of Organic Synthesis and Physico-Chemical Grounds of Catalysis Division of Organic Synthesis and Physico-Chemical Grounds of Catalysis – N 2 Laboratory of Asymmetric Catalysis N 2 – N 8 Laboratory for Catalytic Synthesis N 8 – N14 Laboratory of Development and Study of Polyfunctional Catalysts N14 – N20 Laboratory of Catalysis of Rare and Trace Elements N20 – N24 Laboratory of Catalytic Hydrogenation N24 – N31 Laboratory Polysulfur-Nitrogen Heterocycles N31 – N33 Laboratory for Application of IR, UV-Vis and ESR Spectroscopies in Heterogeneous Catalysis N33 – N34 Laboratory of Electrocatalysis N34 – N35 Laboratory of Academician Kh.M.Minachev N35 – N40 Laboratory of Catalytic Reactions of Carbon Oxides N40 – N47 Laboratory of Catalytic Synthesis of Functionally Substituted Organic N47 – N49 Laboratory for Kinetics of Catalytic Processes N49 – N54 Laboratory for Heterogeneous Catalysts and Catalytic Reactions N54 Division of Computational Chemistry and Modern Information Technologies Division of Computational Chemistry and Modern Information Technologies – N44 Laboratory of Mathematical Chemistry and Computer Design N44 – N50 Laboratory of Computer Assistance to Chemical Research N50 CACR -- General information CACR – N53 (DSTI) Department of Scientific and Technical Information N53 (DSTI) N. D. Zelinsky Institute of Organic Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Directions of research Host Institute

5 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 5 April 3, 2003, Rostock Main Areas of Research The laboratory has a world-wide reputation of the one of the leading centers of carbohydrate research Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Studies of complex carbohydrates of different origin StructuralSynthetic BiosyntheticPhysico-chemical Areas of Research

6 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 6 April 3, 2003, Rostock What is carbohydrate for? Carbohydrate code for biological information! Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research About

7 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 7 April 3, 2003, Rostock Main Areas of Research Before 1994 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Structural and physico-chemical studies Structural studies of bacterial polysaccharides Conformational studies of carbohydrate chains Dr. Yu. A. Knirel Structural studies of glycoproteins Dr. V. A. Derevitskaya Dr. L. M. Likhosherstov Dr. N. P. Arbatsky Structural studies of glycolipids Dr. G. P. Smirnova Dr. G. M. Lipkind Dr. A. S. Shashkov Golden Age Areas of Research

8 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 8 April 3, 2003, Rostock Main Areas of Research Before 1994 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthetic studies Glycosylation methods and synthesis of polysaccharides Synthesis of oligosaccharides and their derivatives Dr. A. Ya. Chernyak Dr. V. I. Torgov Dr. N. E. Nifantiev Dr. A. F. Bochkov Dr. L. V. Backinowsky Dr. V. I. Betaneli Dr. E. M. Klimov Chiral synthons from carbohydrates Dr. A. F. Sviridov Synthesis of neoglycoconjugates Dr. A. Ya. Chernyak Dr. L. M. Likhosherstov Areas of Research Golden Age Special emphasis on this topic

9 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 9 April 3, 2003, Rostock Main Areas of Research Before 1994 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthetic and biosynthetic studies Synthesis of polyprenyl phosphosugars and studies on biosynthesis of bacterial polysaccharides Synthesis of fragments of biopolymers containing glycosyl phosphate residues Dr. V. N. Shibaev Dr. A. V. Nikolaev Dr. V. N. Shibaev Dr. L. L. Danilov Dr. T. N. Druzhinina Areas of Research Golden Age

10 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 10 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Chiral synthons from carbohydrates Previous Achievements Synthesis of aglycons of macrolide antibiotics New syntheses of erythronolides A and B from levoglucosan A. F. Sviridov et al., Tetrahedron 45 (1989) 5109; 47(1991) 2291; 47 (1991) 2317

11 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 11 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Development of new glycosylation methods Previous Achievements Orthoester method (1967) Trityl-cyanoethylidene condensation (1975) Thioorthoester method (1980) Promoter Nucleophile Tr + HgBr 2 Promoter ROTr -Nucleophile CNSRORX R = sugar residue 1,2-trans Dr. A. F. Bochkov Dr. L. V. Backinowsky Dr. V. I. Betaneli

12 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 12 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Development of new glycosylation methods Previous Achievements Orthoester method (1967) Trityl-cyanoethylidene condensation (1975) Thiocyanate condensation (1990) Thioorthoester method (1980) R = sugar residue 1,2-cis Tr + Dr. E. M. Klimov Dr. A. V. Demchenko

13 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 13 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Development of the first general method for regio- and stereoregular synthesis of polysaccharides Previous Achievements Trityl-cyanoethylidene condensation for 1,2-trans-linkages For a review see: N. K. Kochetkov, Tetrahedron 43 (1987) 2389 Thiocyanate condensation for 1,2-cis-linkages For a review see: A. V. Demchenko, Curr. Org. Chem. 7 (2003) 35

14 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 14 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Trityl-cyanoethylidene condensation for 1,2-trans-linkages in polysaccharides Previous Achievements

15 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 15 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Trityl-cyanoethylidene condensation for 1,2-trans-linkages in polysaccharides Previous Achievements

16 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 16 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Chemical synthesis of polysaccharides Previous Achievements Homopolysaccharides Antigenic polysaccharides Block-copolymers Polysaccharides terminated with functionalized aglycon..-6)Glc( )Man( )Glc( )Gal( )Rha( )Gal( )Man( )Rha( )Qui( )GlcA( )Araf( )Araf( )GlcA( )Galf( )Galf( 1-..

17 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 17 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Chemical synthesis of polysaccharides Previous Achievements Homopolysaccharides Antigenic polysaccharides Block-copolymers Polysaccharides terminated with functionalized aglycon..-6)Man( 1-4)Rha( 1-3)Gal( 1-.. Salmonella newington..-3)GlcNAc( 1-2)Rha( 1-2)Rha( 1-2)Rha( 1-.. Shigella flexneri..-6)Galf( 1-3)Galf( 1-3)Galf( 1-.. Salmonella T1..-6)[Gal 1-4]GlcNAc( 1-3)Gal( 1-4)Glc( 1-.. Streptococcus pneumoniae Type 14

18 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 18 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Chemical synthesis of polysaccharides Previous Achievements Homopolysaccharides Antigenic polysaccharides Block-copolymers Polysaccharides terminated with functionalized aglycon H-(-6Man 1-) n -(6Glc 1)-O(CH 2 ) 6 NH 2 H-(6Gal 1) n -(-6Man 1-) m -(6Glc 1)-O(CH 2 ) 6 NH 2 H-[-2)-L-Rha( 1-3)-L-Rha( 1-] n -(6Glc 1)-O(CH 2 ) 6 NH 2 Streptococcus A-variant H-[-3)-D-Rha( 1-2)-D-Rha( 1-3)-D-Rha(a1-] n -(3-D- Rha 1)-O(CH 2 ) 6 NH 2 Pseudomonas aeruginosa common antigen m n

19 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 19 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Major Achievements Before 1994 Chemical synthesis of polysaccharides Previous Achievements Polysaccharides containing 1,2-cis-linkages Thiocyanate condensation for 1,2-cis-linkages

20 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 20 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of oligosaccharides and their derivatives Previous Achievements Glycoconjugates and neoglycocojugates Oligosaccharines (plant hormones) Model compounds for physico-chemical studies Main reasons for the synthesis of oligosaccharides Building blocks for chemical and chemical-enzymic synthesis of polysaccharides

21 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 21 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of oligosaccharides and their derivatives Previous Achievements Different reactivity of hydroxy groups …each oligosaccharide synthesis remains an independent problem whose resolution requires considerable systematic research and a good deal of know-how. H. Paulsen, Angew. Chem., Intern. Ed. 21 (1982) 155. Dependence upon protective group pattern Regioselectivity of glycosylation Main problems during the synthesis of oligosaccharides Stereoselectivity of glycosylation

22 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 22 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of oligosaccharides and their derivatives Previous Achievements Regioselectivity issues A. Ya. Chernyak, L. K. Kononov, P. Radha Krishna, N. K. Kochetkov, Carbohydr. Res. 225 (1992) 279 Fragment of O-specific polysaccharide of Proteus mirabilis O27 Four different types of amino groups

23 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 23 April 3, 2003, Rostock Main Areas of Research After 1995 Due to severe general crisis in Russia in 1990-ies many research lines were abandoned Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Some areas are still being explored Structural analysis of complex carbohydrates Synthetic studies Areas of Research Current Projects The number of researchers dramatically decreased Bacterial polysaccharides Glycoproteins Monosaccharides Oligosaccharides Neoglycoconjugates Polyprenyl and glycosyl phosphate deivatives

24 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 24 April 3, 2003, Rostock 16 steps 11 steps Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of monosaccharides Current Projects Model compounds for structural and physico- chemical studies Stereoisomeric 5,7- diacetamido 3,5,7,9- tetradeoxynonulosonic acids, components of bacterial polysaccarides Dr. Yu. E. Tsvetkov

25 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 25 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of oligosaccharides Current Projects Convergent Synthesis of Fully-Carbohydrate Mannodendrimers L. V.Backinowsky, P. I. Abronina, A. S. Shashkov, A. A. Grachev, N. K. Kochetkov, S. A. Nepogodiev, J. F. Stoddart, Chem. Eur. J. 8 (2002) 4412

26 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 26 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of oligosaccharides Current Projects Convergent Synthesis of Fully-Carbohydrate Mannodendrimers L. V. Backinowsky et al., Chem. Eur. J. 8 (2002) 4412

27 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 27 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of oligosaccharides Current Projects Convergent Synthesis of Fully-Carbohydrate Mannodendrimers Dr. L. V. Backinowsky Current Project: synthesis of 13 C labeled mannodendrimers i PhC(OEt) 3, H + ; ii H 2 O, H + ; iii 1. AgOTf, CH 2 Cl 2 ; 2. MeONa/MeOH

28 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 28 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of oligosaccharides and their derivatives Current Projects Analogs and derivatives of natural lipochitooligosaccharides (nodualtion factors of Rizobium sp. NGR 234) Dr. V. I. Torgov A. I. Zinin Current Project: synthesis of fluorescently labeled pentasaccharides ex 295, 520 nm, em 593 nm

29 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 29 April 3, 2003, Rostock i CH 2 =CHCOOH, TEA, Li 2 PdBr 4, DMF, ii H 2 SO 4, HgSO 4, D, iii Fe/AcOH i HCOOAc, ii Br(CH 2 ) 10 COOMe, Bu t OK, DMF, iii KOH, EtOH-H 2 O, iv H +, v DCC, HOSu/DMF New synthesis of 6-aminophenalenone and its N-alkylation Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Current Projects Dr. V. I. Torgov A. I. Zinin

30 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 30 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of glycosyl phosphate deivatives Current Projects Use of glycosyl nitrates for the preparation of glycosyl phosphates Dr. V. N. Shibaev Dr. P. I. Illarionov

31 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 31 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of neoglycoconjugates Current Projects Dr. L. M. Likhosherstov O. S. Novikova Yields 85-95% New synthesis of glycosylamines using ammonium carbamate

32 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 32 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of neoglycoconjugates Current Projects Dr. L. M. Likhosherstov O. S. Novikova Synthesis of labile glycosylamines

33 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 33 April 3, 2003, Rostock Synthetic Carbohydrate Chemistry Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Synthesis of neoglycoconjugates Current Projects Neoglycoconjugates from glycosylamines Dr. L. M. Likhosherstov O. S. Novikova

34 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 34 April 3, 2003, Rostock Dr. Leonid O. Kononov Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Group of Glycoconjugates (Moscow) Senior research fellow Laboratory of Carbohydrate Chemistry (Moscow) Post-graduate student Prof. N. K. Kochetkov Lund University (Sweden ) Post-doc Prof. G. Magnusson Dr. N. E. Nifantiev RIKEN (Japan) Post-doc Prof. T. Ogawa Prof. V. N. Shibaev Laboratory of Carbohydrate Chemistry (Moscow ) A research group leader

35 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 35 April 3, 2003, Rostock Dr. Leonid O. Kononov Main Areas of Research Since 1992 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Complex natural oligosaccharides and their analogs Sialic acid chemistry Neoglycoconjugates Supramolecular chemistry Areas of Research Universal aglycon Synthesis of neoglycoconjugates Sialylation methods Synthesis of sialooligosaccharides Clusters in solutions Cyclodextrins

36 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 36 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Sialylation without promoter Dr. L. O. Kononov Sialic acid chemistry Current Projects L. O. Kononov, G. Magnusson Acta Chem. Scand. 52 (1998) 141

37 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 37 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Sialylation without promoter Dr. L. O. Kononov Sialic acid chemistry Sialic acid phosphate 88% (from NMR) 78% (after L.C.) : = 5 : 1 80% (from NMR) 76% (after L.C.) Current Projects

38 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 38 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Dr. L. O. Kononov Sialic acid chemistry Polymer-supported sialylation PEG = (OCH 2 CH 2 ) n OMe (M w = 5000) GM4 fragment Current Projects

39 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 39 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Dr. L. O. Kononov Sialic acid chemistry Polymer-supported sialylation Sialic acid donor on a polymer PEG = (OCH 2 CH 2 ) n OMe (M w = 5000) Current Projects

40 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 40 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Dr. L. O. Kononov Sialic acid chemistry Polymer-supported sialylation PEG = (OCH 2 CH 2 ) n OMe (M w = 5000) GM4 fragment + Current Projects L. O. Kononov, Y. Ito, T. Ogawa Tetrahedron Lett. 38 (1997) 1599

41 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 41 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Dr. L. O. Kononov Sialic acid chemistry New synthesis of sialic acid glycal and sulfone L. O. Kononov, B. S. Komarova, N. E. Nifantiev Russ. Chem. Bull., Int. Ed. 51 (2002) 698 Current Projects

42 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 42 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Dr. L. O. Kononov Sialic acid chemistry Synthesis of sialooligosaccharides Ganlioside lactams Synthesis of Ganglioside Lactams Corresponding to GM1-, GM2-, GM3-, and GM4 - Ganglioside Lactones M. Wilstermann, L O. Kononov, U. Nilsson, A. K. Ray, G. Magnusson, J. Am. Chem. Soc. 117 (1995) 4742 GM2 GM3 Current Projects

43 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 43 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Synthesis of sialooligosaccharides Ganlioside lactams Sialyl Le x and sialyl Le a Approaches towards GD3 Dr. L. O. Kononov Sialic acid chemistry Current Projects N. E. Nifantev, Y. E. Tsvetkov, A. S. Shashkov, L. O. Kononov, V. M. Menshov, A. B. Tuzikov, N. V. Bovin J. Carbohydr. Chem. 15 (1996) 939

44 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 44 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Sialylation methods Synthesis of sialooligosaccharides Ganlioside lactams Sialyl Le x and sialyl Le a Approaches towards GD3 Dr. L. O. Kononov Sialic acid chemistry Current Projects

45 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 45 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Allyl as a universal aglycon Dr. L. O. Kononov Neoglycoconjugates Allyl to 2-azidoethyl Allyl to 3-aminopropyl Allyl to propyl Allyl to 2-aminoethyl Removal of allyl Functionalization of allyl Current Projects

46 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 46 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Synthesis of neoglycoconjugates Dr. L. O. Kononov Neoglycoconjugates Amides of uronic acids with amino acids Sialyl Le x and sialyl Le a HNK-1 pentasaccharide Ganlioside lactams Carbohydrate-carborane conjugates for BNCT Current Projects A. V. Kornilov, A. A. Sherman, L. O. Kononov, A. S. Shashkov, N. E. Nifantev, Carbohydr. Res. 329 (2000) 717

47 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 47 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Synthesis of neoglycoconjugates Dr. L. O. Kononov Neoglycoconjugates Amides of uronic acids with amino acids Sialyl Le x and sialyl Le a HNK-1 pentasaccharide Ganlioside lactams Carbohydrate-carborane conjugates for BNCT Current Projects

48 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 48 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal HNK-1 pentasaccharide Dr. L. O. Kononov Synthesis of neoglycoconjugates Current Projects

49 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 49 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Synthesis of neoglycoconjugates Dr. L. O. Kononov Neoglycoconjugates Carbohydrate-carborane conjugates for BNCT Current Projects

50 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 50 April 3, 2003, Rostock Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Areas of Research Personal Dr. L. O. Kononov Supramolecular chemistry Clusters in solutions Conceivably the first example of a phase transition in aqueous solutions of oligosaccharide glycosides. Evidence from variable temperature 1 H NMR and optical rotation measurements for a solution of allyl lactoside L. O. Kononov, D. E. Tsvetkov, A. V. Orlova, Russ. Chem. Bull., Int. Ed., 51 (2002) M 0.4 M Current Projects

51 Laboratory of Carbohydrate Chemistry Head: Professor Vladimir N. Shibaev founded in 1959 by Professor Nikolay K. Kochetkov Host Institute About Previous Achievements Current Projects Areas of Research Personal 51 April 3, 2003, Rostock N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, Moscow, RUSSIA Host Institute